Method of producing a metal-containing single-phase composition

ABSTRACT

A method of producing a single-phase composition M n+1 A z X n , primarily the production of the single-phase material Ti 3 SiC 2 , where n lies within a range of 0.8-3.2, where z lies within a range of 0.8-1.2, where M is at least one metal taken from the group of metals Ti (titanium), Sc (scandium), V (vanadium), Cr (chromium), Zr (zirconium), Nb (niobium) and Ta (tantalum), where X is at least one of the non-metals C (carbon) and N nitrogen), and where A is at least one of the chemical elements Si (silicon), Al (aluminum) and Sn (tin) or a compound of those elements, such that the final, desired compound will include the components M n+1 A z X n . A powder mixture of the components is formed and is ignited under an inert atmosphere to prevent promotion of dissociation and to cause the components to react.

[0001] The present invention relates to a method of producing a metal-containing single-phase, composition. The invention relates primarily to the production of titanium silicon carbide and composite compounds belonging to the same family.

[0002] Oxygen-free combustion synthesis, also known as SHS (Self-propagating High Temperature Synthesis) is used generally in the production of intermetallic products and ceramic compositions.

[0003] In SHS technology, a mixture of two or more materials is ignited locally through the medium of an intensive heat source. This source may, for instance, consist of a heating coil or some other heating element, a laser beam or an electron beam. The local ignition results in a local reaction, as a result of a powerful exothermic reaction. This causes the release of surplus energy, which ignites adjacent part of the material and finally the whole of the material. This chain reaction is very rapid and, when the reaction is controlled, provides a highly effective way of mass-producing intermetals and ceramics. The highest temperature that can be reached by the system is the adiabatic temperature.

[0004] Many attempts to produce Ti₃SiC₂ have been made since the middle of the 1980s. Pampuch et al (R. Pampuch et al, “Solid Combustion Synthesis of Ti₃SiC₂, J. EUR. CERAM. SOC.,5,283-87 (1989)) and others have ignited a powder mixture of Ti, Si and C in an inert atmosphere. This resulted in Ti₃SiC₂+about 10-30% of other phases, such as TiC, TiSi₂ and SiC.

[0005] Goesmann et al (F. Goesmann et al, “Preparation of Ti₃SiC₂ by Electron-Beam-Ignited Solid-State Reaction”, J. Amer. Ceram Soc. 81,11,3025-28 (1998)) believed that SHS would not result in a predominantly single phase consisting of Ti₃SiC₂ due to outgasing of metallic silicon as a result of the extremely high temperature of the reaction, above 2000° C. Goesmann commenced with a mixture of Ti and SiC with a chemical composition of Ti₃SiC₂+12.5 weight-% surplus silicon. He used an electron beam to ignite the mixture. The mixture was treated in three stages, namely heat treatment at 800° C., ignition at 900° C., followed by heat treatment at 1600° C. to achieve outgasing of surplus silicon. This method resulted in less than 8% of secondary phases in the sample.

[0006] In our own U.S. patent application Ser. No. 09/469,893 from December 1999, we have shown that atmospheric oxygen influences the thermic stability of Ti₃SiC₂ in the production process and also in the subsequent sintering process, by forming gaseous SiO, which is fundamentally different to vaporisation of silicon due to high temperatures.

[0007] Thus, it has been found difficult to produce titanium silicon carbide in the aforesaid manner without obtaining other reaction products.

[0008] It has been mentioned above that the invention also relates to compositions in the same family. The family can be designated as being a single phase composition M₃SiZ₂, where M is at least one metal, Z is at least one of the chemical elements C (carbon) and N (nitrogen).

[0009] The present invention relates to the problem of high costs in respect of the production of titanium silicon carbide.

[0010] The present invention thus relates to a method of producing a single-phase composition M_(n+1)A_(z)X_(n), where _(n) lies within a range of 0.8-3.2, where _(z) lies within a range of 0.8-1.2, where M is at least one metal taken from the group of metals Ti (titanium), Sc (scandium), V (vanadium), Cr (chromium), Zr (zirconium), Nb (niobium) and Ta (tantalium), and where X is at least one of the non-metals C (carbon) and N (nitrogen) and where A is at least one of the chemical elements Si (silicon), Al (aluminium) and Sn (tin) or a compound of said elements such as to obtain the components M_(n+1)A_(z)X_(n) of the final desired compound, wherein the method also comprises forming a powder mixture from said metal, non-metal and the last-mentioned chemical element or a compound of said elements, and igniting said powder mixture within an inert atmosphere such as to not promote dissociation, wherewith said ingoing components react, and wherein the method is characterised by causing the reactant temperature to be kept at or above the temperature at which said components are caused to react but beneath the temperature at which the single-phase composition dissociates.

[0011] The invention will now be described in more detail, partly with reference to three examples.

[0012] The method relates to the production of a single-phase (or one-phase) composition M_(n+1)A_(z)X_(n), where _(n) lies within a range of 0.8-3.2, where _(z) lies within a range of 0.8-1.2, where M is at least one metal taken from the group of metals Ti (titanium), Sc (scandium), V (vanadium), Cr (chromium), Zr (zirconium), Nb (niobium) and Ta (tantalium), and where X is at least one of the non-metals C (carbon) and N (nitrogen) and where A is at least one of the chemical elements Si (silicon), Al (aluminium) and Sn (tin) or a compound of said elements such that the final, desired compound will include the components M_(n+1)A_(z)X_(n). The method comprises forming a powder mixture of said metal, non-metal and last-mentioned chemical element or compound, and igniting the powder mixture such that it will react within an inert atmosphere. The inert atmosphere includes an atmosphere that has a sufficiently low partial pressure of oxygen to prevent promotion of dissociation.

[0013] According to the invention, the reaction temperature is caused to be kept at or above a level at which components are caused to react, but beneath the temperature at which the single-phase composition will dissociate.

[0014] Thus, an essential feature of the invention is to realize that-the temperature is kept down. during the reaction, but still above a given level nevertheless.

[0015] This is a preferred method of producing the single-phase composition Ti₃SiC₂.

[0016] According to a highly preferred embodiment, the temperature is kept down by adding pre-reacted Ti₃SiC₂, which material functions as a heat sink.

[0017] Up to about 25 weight-% of Ti₃SiC₂ is preferably used as a heat sink.

[0018] Alternatively, the temperature may be kept down during the reaction in other ways, for instance by controlled cooling of the material.

[0019] Below follows a number of examples.

[0020] Subsequent to heat treating the bed at 1400° C. for eight hours, the bed was found to contain less than 2 weight % TiC.

[0021] This example shows that Si can be used instead of SiC.

[0022] Although the invention has been described above with reference to a number of embodiments thereof, it will be understood that the temperature can be kept within the described range in ways other than described above, within the scope of the present invention.

[0023] The present invention shall therefore not be considered to be limited to the aforesaid exemplifying embodiments, since variations can be made within the scope of the accompanying Claims.

EXAMPLE 1

[0024] Ti, SiC and graphite powder were mixed together to produce a stoichiometric mixture for Ti₃SiC₂. This mixture was mixed with 12 weight-% pre-reacted Ti₃SiC₂.

[0025] The mixture was placed in a reaction vessel through which argon flowed at a rate of 0.5 1/min. The powder bed had a thickness of about 20 cm.

[0026] The bed was ignited by a molybdenum silicide element placed at the bottom of the reaction vessel. The bed components reacted.

[0027] The powder was removed from the vessel, after cooling. The bed could be readily crushed.

[0028] Samples taken from the bed were analysed by means of x-ray diffraction.

[0029] It was established that the bed contained about 2-4 weight-% TiC.

EXAMPLE 2

[0030] Same example as Example 1 but with the exception that 25 weight-% pre-reacted Ti₃SiC₂ was added to the mixture.

[0031] The bed was found to contain 15-20 weight-% TiC subsequent to ignition and cooling.

[0032] Example 2 shows, among other things, that excessive dilution of pre-reactive material results in an incomplete reaction, wherewith the bed requires heat treatment at 1400° C. for eight hours in order to obtain a single-phase material.

EXAMPLE 3

[0033] Same example as Example 2 wherewith Ti, Si and graphite powder were mixed together with 25 weight-% pre-reacted Ti₃SiC₂ and added to the mixture.

[0034] The bed was found to contain 25-30 weight-% TiC, after ignition and cooling. 

1. A method of producing a single-phase composition M_(n+1)A_(z)X_(n), by means of a SHS (Self-propagating High Temperature Synthesis), where _(n) lies within a range of 0.8-3.2, where _(z) lies within a range of 0.8-1.2, where M is at least one metal taken from the group of metals Ti (titanium), Sc (scandium), V (vanadium), Cr (chromium), Zr (zirconium), Nb (niobium) and Ta (tantalium), and where X is at least one of the non-metals C (carbon) and N (nitrogen) and where A is at least one of the chemical elements Si (silicon), Al (aluminium) and Sn (tin) or a compound of said elements such that the final, desired compound will include the components M_(n+1)A_(z)X_(n), wherein the method also comprises forming a powder mixture from said metal, non-metal said chemical element or compound of said elements, and adding the desired compound M_(n+1)A_(z)X_(n) in a pre-reactive state, said material then functioning as a heat sink, and igniting said powder mixture under an inert atmosphere so as to prevent promotion of dissociation, wherewith the components react, and where the method is characterised by keeping the reaction temperature at or above the temperature at which the components are caused to react but beneath the temperature at which the single-phase composition dissociates.
 2. A method according to claim 1, characterised in that n=1, 2 or
 3. 3. A method according to claim 1, characterised in that the single-phase material is Ti₃SiC₂.
 4. A method according to claim 1, characterised in that the single-phase material is Ti₂AlC or Ti₂ SnC.
 5. A method according to claim 1, 2, 3 or 4, characterised by using about 25 weight-% pre-reactive material as a heat sink. 